Europäisches Patentamt *EP001001009B1* (19) European Patent Office Office européen des brevets (11) EP 1 001 009 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C11D 3/395, D06L 3/02, of the grant of the patent: C07F 15/02, C07F 1/08, 03.09.2003 Bulletin 2003/36 C07F 13/00, B01J 31/18 (21) Application number: 98309169.5 (22) Date of filing: 10.11.1998 (54) Bleach and oxidation catalyst Bleich- und Oxidationskatalysator Catalyseur de blanchiment et d’oxydation (84) Designated Contracting States: • Whittaker, Jane DE ES FR GB IT Bebington, Wirral Merseyside CH63 3JW (GB) • Feringa, Bernard Lucas University of Groningen (43) Date of publication of application: Nijenborgh 4 9747 AG Groningen (NL) 17.05.2000 Bulletin 2000/20 • Hermant, Roelant Mathijs Unilever Res. Vlaardingen (73) Proprietors: 3133 AT Vlaardingen (NL) • UNILEVER PLC • Koek, Jean Hypolites Unilever Res. Vlaardingen London EC4P 4BQ (GB) 3133 AT Vlaardingen (NL) Designated Contracting States: • Rispens, Minze Theunis University of Groningen GB Nijenborgh 4 9747 AG Groningen (NL) • UNILEVER N.V. • van Vliet, Ronaldus Theodorus Leonardus 3013 AL Rotterdam (NL) 3133 AT Vlaardingen (NL) Designated Contracting States: DE ES FR IT (74) Representative: Elliott, Peter William et al Unilever plc (72) Inventors: Patent Division • Delroisse, Michel Gilbert Jose Colworth House Bebington, Wirral Merseyside CH63 3JW (GB) Sharnbrook • Hage, Ronald Unilever Research Vlaardingen Bedford MK44 1LQ (GB) 3133 AT Vlaardingen (NL) • Kalmeijer, Robertus Everardus (56) References cited: 3133 AT Vlaardingen (NL) EP-A- 0 458 398 WO-A-95/34628 • Lamers, Christiaan WO-A-97/18035 WO-A-97/48787 Unilever Research Vlaardingen DE-A- 19 605 688 DE-A- 19 713 851 3133 AT Vlaardingen (NL) FR-A- 2 692 499 • Russell, Stephen William, Unilever Vlaardingen 3133 AT Vlaardingen (NL) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 001 009 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 001 009 B1 Description Field of the Invention 5 [0001] This invention relates to bleach and oxidation catalysts, to compositions containing such catalysts, especially bleaching and detergent bleaching compositions, and to methods of bleaching and cleaning substrates, especially fabric substrates, using such catalysts. In particular, the present invention is concerned with catalytic complexes com- prising a pentadentate ligand coordinated to an iron, manganese or copper ion, for use with peroxygen bleaching agents. 10 Background of the Invention. [0002] Peroxygen bleaching agents have been known for many years and are used in a variety of industrial and domestic bleaching and cleaning processes. The activity of such agents is, however, extremely temperature-depend- 15 ent, and drops off sharply at temperatures below 60°C. Especially for cleaning fabrics, high temperature operation is both economically undesirable and practically disadvantageous. [0003] One approach to solving this problem has been through the additional use of so-called bleach activators, also known as bleach precursors. These activators typically are carboxylic acid esters that react with hydrogen peroxide anions in aqueous liquor to generate the corresponding peroxyacid which, in turn, oxidises the substrate. However, 20 these activators are not catalytic. Once the activator has been perhydrolysed, it can no longer be recycled and, there- fore, it is usually necessary to use relatively high levels of activator. Since bleach activators are relatively expensive, the cost of using activators at such levels may be prohibitive. [0004] Another approach has been to use transition metal complexes as catalysts to activate the peroxy bleaching agent. For example, US-A-4,728,455 discloses the use of manganese(III)-gluconate as a peroxide bleach catalyst with 25 high hydrolytic and oxidative stability. In EP-A-0,458,379, for example, triazacyclononane-based manganese complex- es are disclosed that display a high catalytic oxidation activity at low temperatures, which is particularly suitable for bleaching purposes. [0005] In WO-A-9534628, it has been shown that the use of iron complexes containing certain pentadentate nitrogen- containing ligands, in particular N,N-bis(pyridin-2-ylmethyl)-bis(pyridin-2-yl)methylamine ("N4Py"), as bleaching and 30 oxidation catalysts, resulted in favourable bleaching and oxidation activity. However, the synthesis of this ligand is relatively costly. [0006] WO-A-9718035 discloses iron and manganese complexes containing ligands such as N,N'-bis(pyridin-2-yl- methyl)ethylene-1,2-diamine ("Bispicen"), N-methyl-N,N',N'-tris(pyridin-2-ylmethyl)ethylene-1,2-diamine ("Trispic- Meen"), and N,N,N',N'-tetrakis(pyridin-2-ylmethyl)ethylene-1,2-diamine ("TPEN"), as peroxide oxidation catalysts for 35 organic substrates. [0007] WO-A-9748787 relates to iron complexes having polydentate ligands containing at least six nitrogen or oxygen hetero atoms, the metal ion being coordinated by at least five hetero atoms, for example 1,1,4,8,11,11-hexa(pyridin- 2-ylmethyl)-1,4,8,11-tetra-aza-undecane ("Hptu"), as catalysts for peroxide, peroxyacid and molecular oxygen bleach- ing and oxidation. 40 [0008] Whilst known transition metal complexes have to an extent been used successfully as catalysts in bleaching or oxidation processes, there remains a need for other bleaching and oxidation catalysts, preferably that are more effective in terms of activity or cost. [0009] We have now surprisingly found that a significant or improved catalytic activity can be achieved by an iron, manganese or copper complex having a pentadentate ligand comprising substituted heteroaryl groups. Furthermore, 45 we have found that catalysts exhibiting such activity can be produced by easily accessible syntheses. Summary of the Invention [0010] Accordingly, in one aspect, the present invention provides a bleach and oxidation catalyst comprising a com- 50 plex of the general formula (A): z [LMXn] Yq (A) 55 in which M represents iron in the II, III,IV or V oxidation state, manganese in the II, III, IV, VI or VII oxidation state, or copper 2 EP 1 001 009 B1 in the I, II or III oxidation state; X represents a coordinating species; n represents zero or an integer in the range from 0 to 3; z represents the charge of the complex and is an integer which can be positive, zero or negative; 5 Y represents a counter ion, the type of which is dependent on the charge of the complex; q = z/[charge Y]; L represents a pentadentate ligand of general formula (B): 1 1 1 2 10 R R N-W-NR R (B) wherein each R1 independently represents -R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxy- alkylene, aminoalkylene or alkylene ether, and V represents a substituted heteroaryl group selected from pyridinyl, 15 pyrazinyl, pyrazolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W represents an optionally substituted alkylene bridging group selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2-C6H4-CH2-; R2 represents a group selected from alkyl, aryl and arylalkyl, optionally substituted with a substituent selected from + 4 hydroxy, alkoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N (R )3, wherein 20 R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, ami- noalkenyl, alkanyl ether and alkenyl ether. [0011] In another aspect, the present invention provides a bleaching composition comprising a peroxy bleaching compound and a catalyst as defined above. The peroxy bleaching compound is preferably selected from hydrogen 25 peroxide, hydrogen peroxide-liberating or -generating compounds, peroxyacids and their salts, and mixtures thereof. Preferably, the bleaching composition further comprises peroxyacid bleach precursors. [0012] In yet another aspect, the present invention provides a detergent bleach composition comprising a peroxy bleaching compound and a catalyst as defined above, a surface-active material and a detergency builder. [0013] Advantageously, complexes in accordance with the invention have been found to provide favourable stain 30 removal in the presence of hydrogen peroxide or peroxyacids. Also, an improved bleaching activity has been noted, particularly in alkaline aqueous solutions containing peroxy compounds at concentrations generally present in the wash liquor during the fabric washing cycle. The complexes may also provide improved oxidation of organic substrates such as olefins, alcohols and unactivated hydrocarbons. 35 Detailed Description of the Invention [0014] Generally, the metal-complex catalyst of the invention may be used in a bleaching system comprising a peroxy compound, optionally together with a precursor therefor, and is suitable for use in the washing and bleaching of sub- strates including laundry, dishwashing and hard surface cleaning. Alternatively, the metal-complex catalyst of the in- 40 vention may be used for bleaching in the textile, paper and woodpulp industries, as well as in waste water treatment. [0015] As already stated, an advantage of the catalysts according to the present invention is that they exhibit a remarkably high oxidation activity in alkaline